Towards Libraries of Luminescent Lanthanide Complexes and Labels from Generic Synthons

Abstract

A synthetic approach is developed to obtain families of luminescent lanthanide complexes and markers from a generic family of precursors built from nonadentate coordination sites. The syntheses of the precursors, based on a directed regioselective nucleophilic aromatic substitution on polyfluoropyridines, are described. Functionalisation of the synthons on the aromatic moieties allowed the introduction of labelling functions and/or the extension of the electronic delocalisation, with concomitant changes in the spectroscopic properties. The synthesis of two such families of ligands and of some of their complexes of Eu(III) and Tb(III) are described, and the photo-physical properties of the complexes were measured, revealing excellent luminescence quantum yields reaching unity in some cases. For some of these complexes, the emphasis was further put on the preparation of an N-hydroxylsuccinimide (NHS) ester as activated function for labelling. The Tb and La complexes in the NHS activated form were synthesized and fully characterized. The labelling was first demonstrated on amino functionalized polymer beads and characterized by time-resolved luminescence microscopy. In a second step, the activated Tb complex was used for the labelling of GFR44 monoclonal antibody, and was applied to the detection of carcinoembryonic antigene (CEA) within the frame of a time-resolved fluoroimmunoassay. Comparison with a commercially available kit based on a europium cryptate as energy donor confirms the efficiency of Tb to act as an energy donor with an unoptimised 35% increase of the detection efficiency.

Iron(II) Complexes of Tridentate Indazolylpyridine Ligands: Enhanced Spin-Crossover Hysteresis and Ligand-Based Fluorescence

“…17 Although this published method still gave a 1-bip derivative as the major product, we reasoned the milder conditions might give higher yields of the thermodynamically disfavored 2-bip isomer. 18 In this way we have now achieved the synthesis of 2-bip, as well as obtaining the unsymmetric derivatives 2-{indazol-1-yl}-6-(pyrazol-1-yl}pyridine (1-ipp) and 2-{indazol-2-yl}-6-(pyrazol-1-yl}pyridine (2-ipp) in useful quantities for the first time.…”

Detecting free hemoglobin in blood plasma and serum with luminescent terbium complexes

“…S7 for structure) was obtained by modifications of the procedure describe in ref. 28. The concentration of the complex was estimated with absorbance spectroscopy to be 0.5 mg mL À1 .…”

Recent advances in the synthesis and applications of 2,6-dipyrazolylpyridine derivatives and their complexes

“…6 An exception to this generalisation is where indazole reagents are used, when eq 1 yields the more hindered 2,6-di(indazol-1-yl)pyridine products (1-bip, Scheme 1) in moderate 25 yield. 18,19 That reflects the usual reactivity pattern for deprotonated indazoles, which prefer electrophilic attack at N1.…”

“…52,101,[142][143][144][145][146][147][148][149] Appending extra donor groups onto the 3-bpp skeleton gives further scope for high-nuclearity complex formation. Thus, the diphenoxo derivative L 19 66,72,[163][164][165] None of these studies used a chiral bpp derivative as co-ligand, although those are easily accessible for the 1-bpp series. 6 Bubbling O 2 195 The number of miscellaneous complexes of 3-bpp derivatives is much smaller but 10 more varied, [196][197][198][199] and includes manganese(II), 196 samarium(III) 198 and gold(III) 199 compounds.…”